三氟碘甲烷中 ν3-ν6 科里奥利相互作用的再研究

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL
Arun Bhujel, Salma Akter, Muhammad Qasim Ali and G. Barratt Park
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引用次数: 0

摘要

三氟碘甲烷(CF3I)的最低频率基波 ν6 从未在气相中被直接观测和高分辨率分析过。ν6(e)水平通过 b 轴科里奥利相互作用与 286.297 cm-1 处的ν3(a1) 相互作用,从而扰乱了这两个水平的旋转结构。在这项工作中,我们报告了 ν6 振动水平内的低 J 微波跃迁(J 范围为 0-2)。我们在光谱中观察到的 l 型倍增与之前发表的相互作用 ν3-ν6 水平模型的预测结果不一致,这促使我们对模型进行改进。我们进行了ab initio非谐波力场计算,用来约束一些参数,并对一些浮动参数进行检验。我们拟合了由 3593 个跃迁组成的数据集,将我们的测量结果与之前的微波、毫米波和高分辨率红外观测结果结合起来。我们得到了一组合理的拟合参数:ν6 = 267.28 cm-1,但我们不能排除与振动水平结构分析一致的更低值 ν6 = 261.5 cm-1。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Reinvestigation of the ν3–ν6 Coriolis interaction in trifluoroiodomethane†

Reinvestigation of the ν3–ν6 Coriolis interaction in trifluoroiodomethane†

Reinvestigation of the ν3–ν6 Coriolis interaction in trifluoroiodomethane†

The lowest-frequency fundamental ν6 of trifluoroiodomethane (CF3I) has never been directly observed and analyzed at high resolution in the gas phase. The ν6(e) level interacts with ν3(a1) at 286.297 cm−1via a b-axis Coriolis interaction, which perturbs the rotational structure of both levels. In this work, we report low-J microwave transitions (for J ranging from 0–2) within the ν6 vibrational level. The l-type doubling observed in our spectrum agreed poorly with the predictions of previously published models of the interacting ν3ν6 levels, prompting us to refine the model. We performed ab initio anharmonic force-field calculations, which were used to constrain some of the parameters, and which served as a check on some of the floated parameters. We fit a dataset consisting of 3593 transitions, which combined our measurements with previous microwave, millimeter wave, and high-resolution infrared observations. A reasonable set of fit parameters is obtained with ν6 = 267.28 cm−1, but we cannot rule out a lower value of ν6 = 261.5 cm−1 consistent with analyses of the vibrational level structure.

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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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